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Патент USA US3068289

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United States Patent Office
1
B?dilg
Patented Dec. ll, 19%2
2
an alkylating agent in the presence of a Friedel-Crafts
3,068,279
.PURTFHCATION 0F ALKYL ARYL SULFONATES
William L. Groves,,Jr.,and Billy W. Terry, Ponca City,
Okla, assignors to‘ Continental Oil Company, Ponca
City, Okla, a corporation of Delaware
No Drawing. Filed July 20, 1959, ,Ser. No. 828,073
4 Claims; ‘an. ass-sue}
type catalyst such as boron ?uoride, hydrogen ?uoride,
sulfuric acid, etc. The alkylating agent may be a 9 to
18 carbonstraight or branched chain ole?n, alcohol or
halide. A suitable straight or branched chain ole?n is
produced from ‘a ,tetradecane fraction having a boiling
range of 240-260“ C. which is obtained by fractionating
kerosene. Branched chain ole?ns are preferred, hoW~
The present invention relates to the production of
ever, as the alkylating agent, such as the 9 to 18 carbon
neutral alkyl aryl sulfonatcs and relates more particu 10 polymers
of propylene including trimers,'tetramers, pen
larly to the production of neutralized alkyl aryl sulfo
tamers,
or
mixtures ‘thereof. Other alkylating agents ‘that
hates which are substantially free of color bodies.
may be used include the branched chain nonyl, decyl,
Sulfonation of‘ alkyl aryl hydrocarbons has generally
dodecyl, octadecyl alcohols and chlorides.
followed the procedure wherein about 1.3 to 2 parts by
A suitable alkyl aryl hydrocarbon which is also avail
weight of 100 to ‘105 percent sulfuric acid is used per 15 able commercially in large quantities is a. blend of mono
part by weight of the alkyl aryl hydrocarbon. Other
sulfonating agents ‘have been used but whatever agent
was used the resulting mixture upon completion of the
‘sulfonation reaction produced an off-colored sulfonate
upon neutralization with a base such as sodum hydroxide.
Since such colored sulfonates can only be used in a rela
tively few applications, various methods have been sug
gested‘ifor removing the color bodies. Light colored
sulfonates are particularly desirable in‘ a laundry deter
gent. Methods as used heretofore have involved treating
aqueous solutions of metal sulfonates with hydrogen per~
oxide or other bleaching agent such as alkali peroxide.
» Other treating agents have included solutions of a metal
persalt such as an alkali metal perborate, or an alkali
metal persulfate. In addition, aqueous sulfonates have
been blownwith oxygen or oxidizing gas in order to im
prove the color of the product. None of these methods
have been entirely satisfactory, generally because they
have involved an undesirable expenditure of materials
and time and furthermore the product so obtained has
allsylbenzenes sometimes called dodecylbenzene.
This
particular product is‘obtainable from Continental Oil
Company under the trade name “Neolene 400.” Typical
physical properties of dodecylbenzene or “Neolene 400”
are as follows:
‘
Speci?c gravity at 16° C ____________________ __ 0.8742
Average molecular weight __________________ __
232
A.S.T.M., .D—158 Engler distillation:
1.13.? ___________________________ __° F__
5 _______________________________ __° F__
10 ______________________________ __°, F__
F__
50 ______________________________ __°
'90 _______________________________ ___°
97 ______________________________ __°
F.B.P ___________________________ __°
F__
F__
F__
535
545
550
560
580
592
603
Refractive index at 20° C __________________ __ 1.4885
Viscosity at 20° 0, cp ____________________ __
14
Bromine num er _________________________ __
0.16
The sulfonating of the alkyl aryl hydrocarbons may
be carried out by methods well known ‘to ‘those skilled
not been improved'greatly in color.
It is, therefore, a principal object of the present inven
in the art using sulfuric ‘acid or oleum as the sulfonating
tion to provide an improved process which obviates the
agent. Other suitable sulfonating agents which may be
disadvantages of the prior art processes. It is another
used include chlorosulfonic acid, sulfur trioxide, etc. If
object of our invention to provide an improved method 40 desired the alkyl aryl hydrocarbon may be diluted with
for the treatment of alkyl aryl sulfonic acids whereby sub
a solvent such as a mineral oil, halogenated hydrocarbon,
or sulfur dioxide prior to sul-fonation. Sulfur trioxide
tralizing the treated sulfonic acid. Other objects and ad
is the preferred sulfonating ‘agent as the use of this com
‘ vantages of the invention will become apparent from the
45 pound makes it possible to prepare neutralized sulfonate
following description.‘
compositions containing a minimum of inorganic salts.
‘To‘t'he accomplishment of the foregoing and related
When sulfur trioxide is employed there is a tendency to
ends, this invention then comprises the features herein
form sulfonic acid anhydrides and perhaps other similar
after fully described and particularly pointed out in the
products which cause the phenomenon known as “pH
stantially ‘colorless sulfonates may be obtained upon neu
claims, .the following description setting forth in detail
.certain illustrative embodiments of the invention, these
being indicative, however, of but a few of the various
ways in which the principle of the invention may be em
ployed.
reversion” or “acid drift.”
This phenomenon “pl-l reversion” is discussed further
in the co-pending application of James C. Kirk and Edsel
L. Miller entitled “Preparation of Stable Allcaryl Sulfo~
natesf’. Serial No. 480,068, ?led January 5, 1955, now
The foregoing objects and advantages are attained by a
PatentNo. 2,928,867 together‘with means by which this
55
pro ess which in brief involves the following steps: An
reversion can be prevented. The foregoing co-pending
alkyl aryl hydrocarbon is reacted with a's‘ulfonating agent
, such as sulfuric acid, oleum or sulfur trioxide.
Follow
application is assigned to the same assignee to which our
invention is assigned and the‘disclosure of the co-pending
ing sulfonation, the spent sulfonating agent is removed
application is hereby made a part of our application.’
from the mixture comprising the sulfonic acid and the
The bleaching agent employed is hydrogen peroxide
60
spent sulfonating agent. The recovered sulfonic acid is
and suitable quantities of this compound vary from about
, ‘then bleached by treating it with hydrogen peroxide in the
0.1 to 3 Weight percent of 100 percent hydrogen peroxide
presence ‘of a Water soluble organic base. Finally after
based on the weight of the sulfonic acid. Although hy
treatment with‘the hydrogen peroxide,‘ the sulfonic acid
drogen peroxide solutions ranging from about 3 to 100
is neutralized.
‘
percent may be used, we prefer to use a solution having
Before proceeding with ‘specific examples illustrating 65 a concentration ‘of about 30%. As to the temperature
our invention, it: may be well in general to indicate the
nature and the ‘amounts of the materials required in the
process.
during the bleaching process, that may range from about
20 to 75° C., however, We prefer to employ a tempera
ture within a range of about 20‘ to 25° C.
The procedure
Suitable alkyl aryl hydrocarbons which may be used
of bleaching sulfonic acid compositions using hydrogen
are those obtained by ‘the reaction of excess benzene, tolu 70 peroxide is discussed in US. Patent 2,806,055 entitled
vene,, xylene, naphthalene or similar hydrocarbons with
“Puri?cation of Alkaryl Sulfonates” issued to George C.
3,068,279
3
K2Cr2O7 in water and diluting to 100 ml. in a volumetric
?ask. Dissolve 3.2 to 3.3 g. of reagent grade potassium
hydroxide (85 to 86 percent KOH) in approximately 500
Feighner September 10, 1957. The disclosure contained
therein ‘is hereby made a part of the present application.
Suitable organic bases include water soluble amines
ml. of water contained in a one-liter volumetric ?ask.
and urea. Speci?c water soluble amines which We have
found to be highly desirable for use in our process are
Add by pipette 10 ml. of the stock dichromate solution,
triethanolamine and isopropylamine. As to the amount
of the organic base added that may vary from about 1
to 4 weight percent based on the weight of the sulfonic
cool at room temperature, dilute to one liter, and mix
well. Store in a glass-stoppered bottle.
PROCEDURE
acid. A larger quantity of the organic base, of course,
Calculate the weight of sample needed to give 100 ml.
may be used without any detrimental e?ects. These 10 of an aqueous solution containing 4 percent active in
organic bases are relatively expensive and for that reason
gredient. For example, a C-SO slurry with 40 percent
we generally try to use the minimum amount of the or
active calculates 10 g. of slurry per 100 ml. of solution.
ganic base which will still give good results and for that
Weigh (with a precision of 1 percent of sample weight)
reason we prefer to use an amount that varies from about
the calculated amount of slurry into a 100-ml. beaker.
1 to 2 weight percent based on the weight of the sulfonic
Add 25 to 30 ml. of water to the beaker and heat gently
acid.
on a low temperature hot plate, with stirring, until the
In order to disclose the nature of the present invention
slurry is dissolved. Cool and quantitatively transfer the
still more clearly, the following illustrative examples will
solution into a 100-ml. volumetric ?ask. Dilute to 100
be given. It is to be understood that the invention is not
ml.
and mix thoroughly.
to be limited to the speci?c conditions or details set forth 20
Place the No. 42 color ?lter in the Klett, set the slide
in these examples except insofar as such limitations are
for use with rectangular cells, and turn on the light switch.
speci?ed in the appended claims. Parts given are parts
Let the colorimeter “warm up” for 10 to 15 minutes. Fill
by weight.
‘a 4 cm. rectangular cell with distilled water, place the
EXAMPLE 1
cell in the instrument, and adjust to zero reading. Dis
card the water in the cell. Rinse the cell with two small
In this example and the succeeding examples the dodec
portions of the sample solution, ?ll, place the cell in the
ylbenzene sulfonic acid used was prepared by sulfonating
instrument, and obtain the reading. Discard the solution
dodecylbenzene using sulfur trioxide as the sulfonating
and rinse the cell with water, then twice with the standard
agent following the procedure of Example 2 of U.S. Patent
chromate solution. Fill the cell, place in the instrument,
and obtain the reading. Discard the standard solution
and rinse the cell with water and dry.
2,806,055. Two samples of dodecylbenzene sulfonic acid
were prepared. Immediately after preparing the acid 1
part of water was added to 100 parts of the acid to hy
drolyze the anhydrides. Each sample was divided into
CALCULATION
two equal portions, to one portion was added 2 parts of
triethanolamine per 100 parts of the acid two hours after
the addition of the water. All four samples were stored
at room temperature for 42 days. At the end of this
storage period, the acid was neutralized by adding thereto
Calculate the relative color density of the sample solu
tion as follows:
Relative color density (RCD)
: Reading of sample solution
sodium hydroxide. For comparison purposes a sample
of each acid was neutralized prior to the storage period, 40
Reading of standard solution
the salt added to water and the color determined as a
control. In all cases the amount of the salt added to the
water was such that the concentrations of the sodium
sulfonate in water was the same. The experiments to
EXAMPLE 2
In this example dodecylbenzene sulfonic acid was
bleached using 1.5 parts of 30% hydrogen peroxide per
gether with the results are summarized in Table 1 below. 45 100 parts of acid for a period of 20 minutes. The
bleached acid was divided into twelve equal portions, the
Table 1
organic bases in the amounts speci?ed added, and the
acid samples stored for a period of 72 hours at 110° F.
after which the colors of the acid samples were compared
Color
Sample
visually. The results are summarized in Table 2 below.
Acid No 1 Acid No.2
Table 2
Control _____________________________________ __ 0.50 RCD
0.5% RC1)
42 days’ storage no additive used ____________ __ 0.50 RCD
0.70 RCD
42 days’ storage 2 parts triethanolamine added. 0.40 RCD
0.55 RCD
Parts of base added1 per 100 parts 0!
aci
Organic base
55
17 0
2.0
3. 0
4. 0
RCD is an ‘abbreviation of relative color density and is
determined by a method which can be described as
Triefhannlamine
follows:
X
Isopropylaminc _________________________ __
Urea.
OUTLINE OF METHOD
X—Denotes color of about equal intensity.
tion of slurry containing 4 percent active ingredient is
EXAMPLE 3
compared to that obtained on a standard chromate solu~
relative color density (RCD) of the sample.
APPARATUS
Klett~Summerson photoelectric colorimeter
Cell, 4 cm., rectangular
Color ?lter, Klett No. 42
REAGENTS
________________ ..
60
The colorimeter reading obtained on an aqueous solu
tion. The ratio of the two readings is reported as the
x
x
In this example the dodecylbenzene sulfonic acid was
65 divided into four equal portions and the components listed
below added immediately.
Sample No.:
Additive
1 _______________ _. 1% water 2% triethanolamine.
70
2 _______________ _. 1% water 1% urea.
3 _______________ _. 1% water 2% urea.
4- _______________ ... 1% water.
The acid samples were neutralized and the color of the
Standard chromate solution, containing 2 mg. K2Cr2O7
per 100 ml. 0.05 N KCH. Prepare a stock solution of
sulfonate slurries determined. Samples 1, 2, and 3 were
potassium dichromate by dissolving 0.200 g. reagent grade 75 stored man oven at 110° F. for a period. of time varying
3,068,279
from 66 to 330 hours.
The results ‘are summarized
Gravity, APT
below.
Table 3
6
40.4
Average molecular weight _________________ -_
193
Percent sulfonatable ______________________ __
57
A.S.T.M., .D-l58 Engler distillation:
RCD color of sodium sulfonatc slurry
Sample No.
0 hrs.
66 hrs.
0. 64
0. 38
0.45
0. 98
0.80
0. 52
0.5
138 hrs.
330 hrs.
0. 80
0.51
0. 52
0. 91
0. 64
0.71 10
F.B.P. _________________________ __°F-_
488
Refractive index 1at 25 ° C __________________ __ 1.4688
____________________________ _ _
Viscosity at 100° F ____________ __centipoises__
Aniline point ________________________ __°F__
1.33
82
EXAMPLE 4
While particular embodiments of the invention have
In this example the dodecylbenzene sulfonic acid was 15 been described, it will be understood, of course, that the
divided into a plurality of portions the organic base
invention is not limited thereto since many modi?cations
added in parts per 100 parts of acid and then the acid
may be made, and it is, therefore, contemplated to cover
was bleached using varying amounts of hydrogen peroxide
by the appended claims any such modi?cations as fall
after which the di?erent portions were stored for varying
within
the true spirit and scope ‘of the invention.
periods of time at 110° F. The results are summarized 20
The invention having thus been described, what is
below.
claimed and desired to be secured by Letters Patent is:
1. In a method for the preparation of alkyl .aryl sul
[Color in RCD]
fonic acids of improved color comprising (1) reacting
2 parts trietha-
2 parts urea,
1 part urea,
nolamine,
percent bleach
percent bleach
percent bleach
25 an alkyl aryl hydrocarbon wherein said aryl radical is
selected from the group consisting of phenyl, tolyl and
xylyl radicals, and said alkyl radicals contain from 9—18
Hours at 110° F.
carbon atoms therein with a sulfonating agent selected
0.1 0.2 0.35 0.5 0.1 0.2 0.35 0.5 0.1 0.2 0. 35 0.5
.42
.48
.49
.61
.26 .19
.47 .47
.48 .46
.62.G2
.41
.45
.48
.57
.31
.46
.46
.55
.23
.43
.46
.57
.20
.43
.53
.59
.37
.43
.43
.63
.39
.51
.42
.54
.23
.44
.51
.56
from the group consisting of chlorosulfonic acid, sulfur
trioxide, sulfuric acid and oleum, (2) separating spent
.20
.49
.53
.62
sulfonating agent, (3) hydrolyzing any sulfonic acid anhy
drides present with water, (4) bleaching said sulfonic
acid by treatment with 0.1 to 3 weight percent of hydro
gen peroxide, the improvement consisting of adding l-4
35 weight percent of a water soluble organic nitrogen base
EXAMPLE 5
selected from the group consisting of triethanolamine,
Since for practical purposes a 0.35 bleach generally
isopropylamine and urea subsequent to the hydrolysis of
gave the best results, sulfonic acid samples were bleached
any sulfonic acid anhydrides and prior to said bleaching.
before and after aging with the results summarized below.
2. A process according to claim 1 wherein the alkyl
40
Table 5
[Color in ROD]
Hrs at
110° F.
2 parts trlethanolamino, 0.35%
bleach
2 parts urea, 0.35%
1 part urea, 035%
bleach
bleach
aryl hydrocarbon is dodecylbenzene and the sulfonating
agent is sulfur trioxide.
3. In a method for the preparation of ‘alkyl aryl sul
fonates of improved color comprising (1) reacting an
alkyl 'aryl hydrocarbon wherein said aryl radical is se
45 lected from the group consisting of phenyl, tolyl and
xylyl radicals, and said alkyl radicals contain from 9-18
carbon ‘atoms therein with a sulfonating agent selected
from the group consisting of chloro-sulfonic acid, sulfur
Bleached Bleached Bleached Bleached Bleached Bleached
before
after
before
after
before
after
aging
aging
aging
aging
aging
aging
50
0 _____ __
66 ____ __
.26
.47
.26
.27
.23
.43
.23
.25
.23
.44
.23
.27
138-- --
.48
.28
.46
.23
.51
.24
330".--
.62
.44
.57
.31
.56
.35
trioxide, sulfuric ‘acid and oleum, (2) separating spent
sulfonating agent, ( 3) hydrolyzing any sultonic acid anhy
drides present with water, (4) bleaching said sulfonic
acid by treatment with 0.1-3 weight percent of hydrogen
peroxide, and (5) neutralizing said bleached sulfonic acid,
the improvement consisting of adding 14 weight percent
of a water soluble organic nitrogen base selected from
The data reported above show that the organic base
the group consisting of triethanolamine, isopropylamine
may be added with the water prior to bleaching if desired.
and urea subsequent to the hydrolysis of any sulfonic acid
In fact, in many cases that is the preferred procedure.
anhydrides and prior to said bleaching.
These data also show that it is much better to bleach the
4. A method according to claim 3 wherein the alkyl
acid just prior to use rather than bleach immediately
after preparing the acid and then ‘storing it until it is used. 60 aryl hydrocarbon is dodecylbenzene and the sulfonating
agent is sulfur trioxide.
Although the examples given above are speci?c to
dodecylbenzene sulfonic acid our invention is not so
References Cited in the ?le of this patent
limited but can be used for the improvement in color of
UNITED STATES PATENTS
other sulfonic acids. As an vadditional example the
product known as dodecylbenzene intermediate sulfonic
2,805,249
Gilbert et a1. __________ __ Sept. 3, 1957
acid is improved in color by the procedure of this inven
2,806,055
Feighner ____________ .... Sept. 10, 1957
tion. Dodecylbenzene intermediate sulfonic acid is ob
2,827,484
Carlson etal ___________ _. Mar. 18, 1958
tained by sulfonating the hydrocarbon known as dodecyl
benzene intermediate. Its typical physical properties are
as follows:
FOREIGN PATENTS
70
88,982
Netherlands __________ _... Aug. 15, 1958
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